Azo compounds having 2,4-disubstituted-3-halothienyl-5-diazo component radicals, dyeing processes therewith and substrates dyed therewith

ABSTRACT

Compounds of the formula ##STR1## wherein R is halo, 
     R 1  is cyano; (C 1-6  alkoxy)carbonyl; (C 3-6  alkenyl)oxycarbonyl; C 1-4  alkylsulfonyl; phenylsulfonyl; (C 1-4  alkyl)carbonyl; benzoyl; carbamoyl; (C 1-4  alkyl)carbamoyl; N,N-di-(C 1-4  alkyl)carbamoyl; phenylcarbamoyl; benzyloxycarbonyl; or (C 1-6  alkoxy)carbonyl, (C 3-6  alkenyl)oxycarbonyl, C 1-4  alkylsulfonyl, phenylsulfonyl or (C 1-4  alkyl)carbamoyl substituted by one or two substituents independently selected from chloro, bromo, C 1-4  alkyl, C 1-4  alkoxy, hydroxy, cyano and acyl, and 
     R 2  is formyl, cyano, --CH═C(R 4 ) 2  or --CH═N--OH, 
     wherein (1) each R 4  is independently cyano; (C 1-6  alkoxy)carbonyl; (C 3-6  alkenyl)oxycarbonyl; (C 3-6  alkynyl)oxycarbonyl; or (C 1-6  alkoxy)carbonyl, (C 3-6  alkenyl)oxycarbonyl or (C 3-6  alkynyl)oxycarbonyl substituted by one or two substituents independently selected from chloro, bromo, C 1-4  alkyl, C 1-4  alkoxy, hydroxy, cyano and acyl, 
     (2) one R 4  is cyano and the other is benzoyl or benzoyl monosubstituted by (C 1-4  alkoxy)carbonyl, C 1-4  alkylsulfonyl, phyenylsulfonyl, carbamoyl, (C 1-4  alkyl)carbamoyl, phenylcarbamoyl or (C 1-4  alkoxy)carbonyl, C 1-4  alkylsulfonyl, phenylsulfonyl or (C 1-4  alkyl)carbamoyl substituted by one or two substituents independently selected from chloro, bromo, C 1-4  alkyl, C 1-4  alkoxy, hydroxy, cyano and acyl, 
     (3) one R 4  is hydrogen and the other is benzoyl; benzoyl monosubstituted by (C 1-2  alkoxy)carbonyl, halo, C 1-4  alkyl, nitro or (C 1-2  alkoxy)carbonyl substituted by one or two substitutents independently selected from chloro, bromo, C 1-4  alkyl, C 1-4  alkoxy, hydroxy, cyano and acyl; (C 1-4  alkyl)carbonyl or (C 3-6  alkenyl)carbonyl or 
     (4) one R 4  is nitro and the other is hydrogen, methyl or ethyl, and 
     R 3  is amino or --N═N--K, wherein K is a coupling component radical. 
     The compounds wherein R 3  is --N═N--K are useful as disperse dyes and those wherein it is amino are useful as intermediates in the synthesis of those wherein it is --N═N--K.

This is a continuation-in-part of application Ser. No. 07/157,441, filedFeb. 17, 1988 and now abandoned which is a continuation of applicationSer. No. 06/920,818, filed Oct. 17, 1986 and now abandoned, which is acontinuation of application Ser. No. 06/771,277, filed Aug. 30, 1985 andnow abandoned.

The invention relates to thiophene ring-containing compounds useful asdisperse dyes or for preparing disperse dyes.

According to the invention there is provided compounds of formula I##STR2## in which R is halogen,

R₁ is cyano, C₁₋₆ alkoxycarbonyl, C₃₋₆ alkenyloxycarbonyl,aminocarbonyl, C₁₋₄ alkylsulphonyl, phenylsulphonyl, C₁₋₄ alkyl- orphenyl-carbonyl, phenyl-, mono-C₁₋₄ alkyl- or di-C₁₋₄alkyl-aminocarbonyl or benzyloxycarbonyl;

R₂ is formyl, cyano, --CH═C(R₄)₂ or --CH═N--OH; and

R₃ is --N═N--K or --NH₂ ; wherein K is a coupling component radical;each R₄ independently is cyano, C₁₋₆ alkoxycarbonyl, C₃₋₆alkenyloxycarbonyl or C₃₋₆ alkynyloxycarbonyl; or one R₄ is cyano andthe other R₄ is benzoyl unsubstituted or monosubstituted by C₁₋₄alkoxycarbonyl, C₁₋₄ alkylsulphonyl, phenylsulphonyl or aminocarbonylunsubstituted or monosubstituted by C₁₋₄ alkyl or phenyl; or one R₄ ishydrogen and the other R₄ is benzoyl unsubstituted or monosubstituted byC₁₋₂ alkoxycarbonyl, halogen, C₁₋₄ alkyl or --NO₂ ; C₁₋₄ alkylcarbonylor C₃₋₆ alkenylcarbonyl; or one R₄ is nitro and the other R₄ ishydrogen, methyl or ethyl.

In R₁ and R₄ any alkoxycarbonyl, alkenyloxycarbonyl,phenoxyalkylcarbonyl, phenoxycarbonyl, alkylaminocarbonyl,alkylsulphonyl, phenylsulphonyl or alkynyloxycarbonyl is unsubstitutedor substituted by 1 or 2 substituents independently selected from Cl,Br, C₁₋₄ alkyl, C₁₋₄ alkoxy, hydroxy, cyano and acyl, for example##STR3## preferably not more than 1, unless indicated to the contrary.Preferably, any such group is unsubstituted, unless indicated to thecontrary.

For the avoidance of doubt, any group capable of being linear orbranched is linear or branched unless indicated to the contrary.

In this specification, halogen is chloro or bromo, more preferablychloro.

Preferably any alkyl group is C₁₋₂ alkyl.

Preferably any alkenyl group is C₃₋₄ alkenyl.

Preferably any alkoxy group is C₁₋₂ alkoxy.

Preferably any alkynyl group is C₃₋₄ alkynyl.

In the compounds of formula I preferably R₁ is R₁ ', where R₁ ' iscyano, C₁₋₄ alkoxycarbonyl, C₃₋₄ alkenyloxycarbonyl, C₁₋₄ alkoxy- C₂₋₄alkoxycarbonyl, benzyloxycarbonyl, monoC₁₋₄ alkylaminocarbonyl, C₁₋₄alkylsulphonyl or phenylsulphonyl. More preferably R₁ is R₁ ", where R₁" is cyano, C₁₋₂ alkoxycarbonyl, monoC₁₋₂ alkylaminocarbonyl, C₁₋₂alkylsulphonyl or phenylsulphonyl. Most preferably R₁ is R₁ "', where R₁"' is cyano or C₁₋₂ alkoxycarbonyl.

R₂ is preferably R₂ ', where R₂ ' is formyl, cyano, --CH═C(R₄ ')₂, whereeach R₄ ' independently is cyano, C₁₋₆ alkoxycarbonyl, C₃₋₆alkenyloxycarbonyl or (2-C₁₋₄ alkoxyethoxy)carbonyl or one R₄ ' is nitroand the other R₄ ' is hydrogen. More preferably R₂ is R₂ ", where R₂ "is formyl or cyano. Most preferably R₂ is formyl.

R₄ is preferably R₄ ' defined above, more preferably R₄ ", where one R₄" is cyano and the other R₄ " is C₁₋₆ alkoxycarbonyl.

K is preferably K', where K' is a coupling component radical of theaniline, α-naphthylamine, pyrazole, aminopyrazole, indole,tetrahydroquinoline, thiazole, phenol, naphthol, benzomorpholine orpyridine series. More preferably K is K", where K" is a group of formulaa ##STR4## in which

R₅ is hydrogen; C₁₋₂ alkyl; C₁₋₂ alkoxy; formylamino; C₁₋₄alkylcarbonylamino in which the alkyl group is unsubstituted ormonosubstituted by hydroxy, chloro, bromo, C₁₋₄ alkoxy, phenyl, phenoxy,benzyloxy, C₁₋₂ alkylcarbonyloxy or C₁₋₂ alkoxycarbonyl; benzoylamino(preferably by other than C₁₋₂ alkylcarbonyloxy); acryloylamino;aminocarbonylamino; C₁₋₄ alkylaminocarbonylamino; C₁₋₄alkoxycarbonylamino in which the alkoxy group is unsubstituted ormonosubstituted by C₁₋₂ alkoxy or phenyl; C₁₋₂ alkyl- orphenyl-sulphonylamino; di-(C₁₋₂ alkyl)aminosulphonylamino; fluoro;chloro or bromo;

R₆ is hydrogen fluoro, chloro, bromo, C₁₋₂ alkyl, C₁₋₄ alkoxy or C₁₋₂alkoxyethoxy, provided that when R₅ is fluoro, chloro or bromo, R₆ isother than fluoro, chloro and bromo;

R₇ is hydrogen; C₁₋₁₀ alkyl; C₂₋₁₀ alkyl monosubstituted by chloro,bromo, hydroxy, cyclohexyl, -SCN, cyano, C₁₋₄ alkylcarbonyl, C₁₋₄alkoxycarbonyl, formyloxy, C₁₋₁₀ alkylcarbonyloxy, chloro- or bromo-C₁₋₃ alkylcarbonyloxy, C₁₋₁₀ alkoxycarbonyloxy, C₁₋₂alkoxyethoxycarbonyloxy, C₃₋₄ alkenyloxycarbonyl, chloro- orbromo-allyloxycarbonyl, C₃₋₄ alkenyloxy, chloro- or bromo- allyloxy,C₃₋₄ alkynyloxy, benzoyloxy, benzyloxy, C₁₋₁₀ alkoxy, phenyl, phenoxy,phenyl(C₁₋₄ alkoxy), (C₁₋₂ alkoxy)ethoxycarbonyl or benzyloxycarbonyl(preferably by other than benzyloxy); C₂₋₁₀ alkyl disubstituted bychloro, bromo, hydroxy, formyloxy, (C₁₋₄ alkyl)carbonyloxy, chloro- orbromo-(C₁₋₃ alkyl)carbonyloxy, (C₁₋₄ alkoxy)carbonyloxy, (C₁₋₂alkoxy)ethoxycarbonyloxy, chloro- or bromo-allyloxycarbonyl, C₃₋₄alkynyloxy or (C₁₋₂ alkoxy)ethoxycarbonyl; C₁₋₄ alkoxyC₂₋₆ alkyl inwhich the alkyl moiety of the alkoxy is monosubstituted by chloro,bromo, cyano, C₁₋₄ alkoxy, alkoxy, C₁₋₄ alkoxycarbonyl, C₁₋₄alkoxycarbonyloxy or C₁₋₄ alkylcarbonyloxy; β-(C₁₋₄alkoxycarbonylmethoxycarbonyl)ethyl; C₃₋₄ alkenyl, unsubstituted ormonosubstituted by phenyl, chloro or bromo; propynyl; C₅₋₇ cycloalkyl;cyclohexyl mono-, di- or tri-substituted by methyl; phenyl,unsubstituted or monosubstituted by chloro, bromo, nitro or C₁₋₄ alkoxyor mono-, di- or tri-substituted by methyl; or β-hydroxypropylmonosubstituted by γ-C₁₋₄ alkoxy, γ-C₃₋₄ alkenyloxy or γ-phenoxy; and

R₈ is hydrogen; C₁₋₁₀ alkyl; C₂₋₁₀ alkyl monosubstituted by chloro,bromo, hydroxy, cyano, -SCN, C₁₋₁₀ alkylcarbonyl, C₁₋₁₀ alkoxycarbonyl,formyloxy, C₁₋₁₀ alkylcarbonyloxy, chloro- or bromo-C₁₋₄alkylcarbonyloxy, C₁₋₁₀ alkoxycarbonyloxy, C₁₋₂ alkoxyethoxycarbonyloxy,C₃₋₄ alkenyloxycarbonyl, chloro- or bromo-allyloxycarbonyl, C₃₋₄alkenyloxy, chloro- or bromo-allyloxy, C₃₋₄ alkynyloxy, benzoyloxy,benzyloxy, C₁₋₁₀ alkoxy, phenyl, phenoxy, phenyl C₁₋₄ alkoxy,aminocarbonyl, mono-C₁₋₄ alkyl- or di-(C₁₋₄ alkyl)aminocarbonyl,mono-C₁₋₄ alkyl- or di-(C₁₋₄ alkyl)aminocarbonyloxy,phenylaminocarbonyl, phenylaminocarbonyloxy, phthalimidyl-2,succinimidyl-2, saccharinyl-2, pyridyl, benzothiazolyl-2-mercapto, (C₁₋₂alkoxy)ethoxycarbonyl or benzyloxycarbonyl (preferably by other thanbenzyloxy); C₂₋₁₀ alkyl disubstituted by chloro, bromo, -OH, formyloxy,(C₁₋₄ alkyl)carbonyloxy, chloro- or bromo-(C₁₋₃ alkyl)carbonyloxy, (C₁₋₄alkoxy)carbonyloxy, (C₁₋₂ alkoxy)ethoxycarbonyloxy, chloro- orbromo-allyloxycarbonyl, C₃₋₄ alkynyloxy or (C₁₋₂ alkoxy)ethoxycarbonyl;C₁₋₄ alkoxyC₂₋₄ alkyl, in which the alkyl moiety of the alkoxy ismonosubstituted by chloro, bromo, cyano, C₁₋₄ alkoxy, C₁₋₄alkoxycarbonyl, C₁₋₄ alkoxycarbonyloxy or C₁₋ 4 alkylcarbonyloxy; orC₃₋₄ alkenyl unsubstituted or monosubstituted by phenyl, chloro orbromo; or

R₇ and R₈ together with the N-atom to which they are attached formunsubstituted piperidine or unsubstituted morpholine;

or K" is a group of formula b, c, d, or e ##STR5## where R₉ is hydrogen,C₁₋₄ alkyl or phenyl unsubstituted or mono- or di-substituted by methyl,methoxy or chloro, and R₅, R₇ and R₈ are as defined above.

When any significance of R₇, R₈ or R₉ bears two substituents, they maybe the same or different.

Preferably R₅ is R₅ ', where R₅ ' is hydrogen, C₁₋₂ alkyl or C₁₋₂alkylcarbonylamino; more preferably R₅ is R₅ ", where R₅ " is hydrogen,methyl or acetylamino.

Preferably R₆ is R₆ ', where R₆ ' is hydrogen or C₁₋₂ alkoxy.

Preferably R₇ is R₇ ', where R₇ ' is C₁₋₆ alkyl, C₁₋₄ alkoxyC.sub. 2-4alkyl, C₃₋₄ alkenyloxyC₂₋₄ alkyl, C₁₋₂ alkylcarbonyloxyC₂₋₄ alkyl, C₁₋₄alkoxycarbonylC₂₋₄ alkyl, allyl, C₁₋₂ alkoxycarbonyloxyC₂₋₄ alkyl orphenoxyC.sub. 2-4 alkyl; more preferably R₇ is R₇ ", where R₇ " is C₂₋₄alkyl, 2-C₁₋₂ alkoxyethyl or allyl.

Preferably, in R₇ and R₈ any hydroxy, thiocyano, cyano, acyloxy (e.g.,formyloxy, alkylcarbonyloxy and alkoxyethoxycarbonyloxy), alkenyloxy,haloallyloxy, alkynyloxy, alkoxy, phenoxy or substituted alkoxy (e.g.phenylalkoxy and chloroalkoxy) on an alkyl group or moiety attached to anitrogen or oxygen atom is in other than the 1-position thereof and notwo such substituents are attached to a single carbon atom. Morepreferably, any other non-hydrocarbyl substituent is also in other thanthe 1-position.

Preferably R₈ is R₈ ', where R₈ ' is hydrogen, C₂₋₄ alkyl, C₁₋₄alkoxyC₂₋₄ alkyl, C₃₋₄ alkenyloxyC₂₋₄ alkyl, allyl, hydroxyC₂₋₄ alkyl,C₁₋₂ alkoxycarbonyloxyC₂₋₄ alkyl or C₁₋₂ alkylcarbonyloxyC₂₋₄ alkyl;more preferably R₈ is R₈ ", where R₈ " is hydrogen, C₂₋₄ alkyl,2-hydroxyC₂₋₄ alkyl or allyl.

In R₇ ' and R₈ ' any C₁₋₄ alkoxy, C₃₋₄ alkenyloxy, (C₁₋₂alkyl)carbonyloxy, (C₁₋₂ alkoxy)carbonyloxy, phenoxy or hydroxysubstituent on a C₂₋₄ alkyl group is in other than the 1-position.Preferably, any other substituent on a C₂₋₄ alkyl group is also in otherthan the 1-position.

Preferably, in R₇, R₇ ', R₈ and R₈ ' the double or triple bond of anyalkenyl or alkynyl group attached to a nitrogen or oxygen atom is inother than the 1-position.

Preferably K" is a group of formula a defined above.

More preferably K is K"', where K"' is a group of formula a' ##STR6##wherein R_(5a) ' is hydrogen, C₁₋₂ alkyl, C₁₋₂ alkylcarbonylaminounsubstituted or monosubstituted by C₁₋₄ alkoxy or chloro, or C₂₋₄alkenylcarbonylamino;

R₆ ' is hydrogen or C₁₋₂ alkoxy;

R_(7a) ' is C₁₋₆ alkyl, C₁₋₄ alkoxyC₂₋₄ alkyl, C₃₋₄ alkenyloxyC₂₋₄alkyl, C₁₋₂ alkylcarbonyloxyC₂₋₄ alkyl, C₁₋₄ alkoxyC₂₋₄ alkyl, allyl,C₁₋₂ alkoxycarbonyloxyC₂₋₄ alkyl, benzyloxy-C₂₋₄ alkyl or phenoxyC₂₋₄alkyl; and

R_(8a) ' is hydrogen, C₂₋₄ alkyl, C₁₋₄ alkoxyC₂₋₄ alkyl, C₃₋₄alkenyloxyC₂₋₄ alkyl, allyl, hydroxyC₂₋₄ alkyl, C₁₋₂alkoxycarbonyloxy-C₂₋₄ alkyl, C₁₋₂ alkylcarbonyloxyC₂₋₄ alkyl, phenylC₁₋₃ alkyl, γ-C₃₋₄ alkenyloxy-β-hydroxypropyl orγ-phenoxy-β-hydroxypropyl.

Most preferably K is K"", where K"" is 2-methyl-4-(N,N-di-C₂₋₄alkylamino)phenyl,2-methyl-4-(N-ethyl-N-γ-ethoxycarbonylpropylamino)phenyl,2-methyl-4-(N-ethyl-N-γ-phenoxypropylamino)phenyl,2-acetylamino-4-(N-β-ethoxycarbonylethylamino)-5-ethoxphenyl,2-acetylamino-4-(N-ethyl-N-allyl-amino)-5-ethoxyphenyl,2-methyl-4-(N-ethyl-N-β-hydroxybutylamino) phenyl,2-acetylamino-4-(N,N-di-C₂₋₃ -alkylamino)phenyl,2-acetylamino-4-(N,N-di-C₂₋₄ alkylamino)-5-C₁₋₂ -alkoxyphenyl, 2-C₁₋₂alkoxyacetylamino-4-(N,N-di-C₂₋₃ alkylamino)phenyl,2-acetylamino-4-(N-ethyl-N-ethoxycarbonylethylamino)-5-methoxyphenyl,2-acetylamino-4-(N-1'-chloroallyl-N-ethoxycarbonylethylamino)-5-methoxyphenyl,2-acryloylamino-4-(N,N-dipropylamino)phenyl,2-benzoylamino-4-(N,N-di(β-methoxyethylamino)phenyl,2-methyl-4-(N,N-di-4'-acetoxy-n-butylamino)phenyl,2-methyl-4-(N-ethyl-N-4'-acetoxy-n-butylamino)phenyl,2-methyl-4-(N-ethyl-N-β-benzyloxyethylamino)-phenyl,2-methyl-4-(N-ethyl-N-β-hydroxy-γ-allyloxypropylamino)phenyl;2-methyl-4-(N-ethyl-N-β-hydroxy-γ-phenoxypropylamino)phenyl,2-methyl-4-(N,N-di-γ-ethoxycarbonylpropylamino)phenyl,2-methyl-4-(N-ethyl-N-γ-cyanopropylamino)phenyl or2-methyl-4-(N-methyl-N-γ-phenylpropylamino)phenyl (especially the firsteight significanes)

Preferred compounds of formula I are those of formula II or III ##STR7##more preferably of formula III.

Preferred compounds of formula III are of formula III' ##STR8##

The more preferred compounds of formula III are of formula III" ##STR9##where K"" is defined above.

Compounds of formula I in which R₃ is --N═N--K can be prepared bycoupling to a diazotised compound of formula I where R₃ is --NH₂ acompound of formula V

    H--K                                                       (V)

where the symbols are as defined above.

Compounds of formula I in which R₃ is --NH₂ can be prepared by reactinga compound of formula VI ##STR10## in which R₁ is defined above and R₁₀is a primary amino group, --NHCHO or --NHCOC₁₋₄ alkyl, with a Vilsmeierreagent to form a compound of formula VII ##STR11## followed byhydrolysis of R₁₀ to form --NH₂ and optional conversion of the formylgroup to any of the other significances of R₂.

Preferably the Vilsmeier reagent is the reaction product of phosphorusoxychloride and dimethylformamide in which case the compound of formulaVII formed is of the formula ##STR12## which is then hydrolysed in acidor basic medium to a compound of formula I in which R₂ is formyl and R₃is --NH₂.

Compounds of formulae V and VI are known or may be made by known methodsfrom known compounds. Vilsmeier reagents are also known.

Conversion of the formyl group to another significance of R₂ in formulaI can be carried out conventionally, for example by condensation withhydroxylamine and optional acylation on the oxygen alone whilst formingthe nitrile group or reaction according to the Knoevenagel or Perkinreaction.

It is particularly preferred that the compounds of formula I contain nowater-solubilizing groups.

The compounds of formula I in which R₃ is --N═N--K will hereinafter bereferred to as the dyes of formula I. They are excellent disperse dyes.

The dyes of formula I can be worked up into dyeing preparations in knownways, for example by milling in the presence of dispersing agent orfilling material. The preparation so produced (which may be dried invacuum or by spray-drying) can be used in a long or short dyebath fordyeing, padding or printing material.

The dyes of the invention exhaust onto synthetic or semisynthetichydrophobic high molecular weight textile material very well from anaqueous suspension. The dyes of the invention are particularly usefulfor dyeing, padding or printing textile material made from lineararomatic polyester, cellulose 21/2 acetate, cellulose triacetate orsynthetic polyamide.

Dyeing, printing or padding can be carried out by known methods, inparticular according to the methods described in UK Patent 1,114,433.

The resulting dyeings have good fastness properties, in particular goodlight fastness, good thermofixation, good sublimation fastness and goodfastness to pleating.

Many of the azo compounds of formula I, in particular those in which R₁is cyano, have an additional advantage over the known thiophene-2-azodisperse dyes in that they give brillant neutral to greenishblue-coloured dyeings having attractive hues comparable with theexpensive anthraquinone dyes. In these azo compounds, halogen(especially chlorine) as the substituent R produces a surprisingly largebathochromic shift in comparison to the known thiophene-2-azodispersedyes with hydrogen or alkyl as the substituent R in the same position.The dyeings of azo compounds of formula I in which R is halogen(especially chlorine) are also characterised by a favorable behaviorunder artificial light, which is a clear advantage compared with adyeing (same hue under daylight) of the known thiophene-2 azo dyes inwhich R is methyl or hydrogen; these latter dyeings are characterized bya strong undesired red shift under artificial light.

The invention will now be illustrated by the following Examples in whichall parts and percentages are by weight and all temperatures are in °C.

EXAMPLE 1

37.5 Parts of 2-amino-3-ethoxycarbonyl-4-oxo-4,5-dihydrothiophene(described in J. Org. Chem. 38 (20), 3615 [1973]) are dissolved in 152parts of dimethylformamide, cooled to -10° C. and to this solution 90parts of phosphorus oxychloride are added whilst stirring well. Thismixture is heated to 70° and allowed to cool and is then poured onto 500parts of ice water. The temperature of the mixture rises to 40° C. Themixture is stirred for 1/2 hour, cooled to 5° C. and filtered and theresidue is washed with a little ice water. The resulting compound is2-dimethylamino methylimino-3-ethoxycarbonyl-4-chloro-5-formylthiophene,m.p. 197° C. The product is suspended in 500 parts of water and 25 partsof 85% phosphoric acid are added together with 395 parts of ethylalcohol and 60 parts of 30% sodium hydroxide. Over two hours and whilststirring the temperature of the suspension is raised to 65°-70° C. andthe pH is maintained at 9 by addition of sodium carbonate. This is thendiluted with 300 parts of ice water and the pH is brought to 6.5 by theslow addition of 30% HCl (about 23 parts).2-Amino-3-ethoxycarbonyl-4-chloro-5-formylthiophene precipitates, m.p.176°-178°. The product is filtered and washed with a little ice-water.The pure product is recrystallised from ethanol/water, m.p. 180° C.

By reacting the 5-formyl compound with a methylene active compound,derivatives of this product can be produced by known methods.

EXAMPLE 2

a) 122 Parts of 1,1-dicyano-2-methoxypropene together with 32 parts ofsulphur powder are suspended in 300 parts of N,N-dimethylformamide,cooled to about 10° and 52 parts of triethylamine are added dropwiseover 30 minutes whilst stirring. The temperature of the reaction mixtureis allowed to rise to room temperature (25°) and the solution of2-amino-3-cyano-4-methoxythiophene so formed is poured after stirringfor 3 to 4 hours onto 500 g of ice and 150 parts of conc. hydrochloricacid. The mixture that results is stirred 1 to 2 hours and is filtered;the product is 2-amino-3-cyano-4,5-dihydrothiophene-4-one. This iswashed with water and then dried.

b) 70 Parts of the product prepared in a) above is dissolved in 400parts of N,N-dimethylformamide and 230 g of phosphorus oxychloride isadded, dropwise over 15 minutes at 5°. Whilst stirring, the reactiontemperature is allowed to rise and the mixture is heated to 70° andafter 3 to 4 hours is poured onto 1000 parts of ice. Finally, themixture is neutralised to a pH of about 6 by adding about 450 parts of25% ammonia and the product2-(N,N-dimethylformamidino)-3-cyano-4-chloro-5-formylthiophene, m.p.183° to 188°, is filtered off. The product is recrystallised fromacetonitrile, m.p. 191.5° to 193° C.

c) 24.15 Parts of2-(N,N-dimethylformamidino)-3-cyano-4-chloro-5-formylthiophene aresuspended in 100 parts of 50% formic acid. 1 Part of ammonium sulphateis added and the mixture is boiled under reflux for about 5 hours. Themixture is allowed to cool and the product,2-amino-3-cyano-4-chloro-5-formylthiophene, is filtered off. The amine,without further purifying, is diazotised (as described in Example 16)and coupled. The pure product is recrystallised from a mixture ofethanol and water, m.p. 267° to 269°.

By condensation of the 5-formyl group by known methods (i.e. Knoevenagelreaction, oxime formation and dehydration) derivatives of this compoundcan be made. Formation of derivatives can be done when the azo compoundhas already been formed (as described in Example 17).

EXAMPLES 3 to 15

Compounds of the formula ##STR13## in which R₁ and R₂ are defined inTable 1 below, can be formed analogously to the method of Example 1 or 2from suitable reactants.

                  TABLE 1                                                         ______________________________________                                        EX.                                                                           No.  R.sub.2              R.sub.1                                             ______________________________________                                        3    CHO                  COOCH.sub.3                                         4    "                    COOC.sub.4 H.sub.9                                  5    "                    COOCH.sub.2 CH.sub.2 OCH.sub.3                      6    "                    COOCH.sub.2 C.sub.6 H.sub.5                         7    "                    SO.sub.2 C.sub.6 H.sub.5                                  ##STR14##           CN                                                  9                                                                                   ##STR15##           "                                                   10   CHO                  CONH-n-C.sub.4 H.sub.9                              11   CN                   CN                                                  12   "                    COOC.sub.2 H.sub.5                                  13                                                                                  ##STR16##           CN                                                  14                                                                                  ##STR17##           "                                                   15                                                                                  ##STR18##           "                                                   ______________________________________                                    

EXAMPLE 16

23.5 Parts of 2-amino-3-ethoxycarbonyl-4-chloro-5-formylthiophene aredissolved in a mixture of 400 parts acetic acid, 100 parts of propionicacid and 85 parts of phosphoric acid at 30°, then cooled to -5° and atthis temperature reacted with 7.0 parts of sodium nitrite (in the formof a 4N solution) at this temperature. A brown solution results. This isstirred for about 2 hours. To this diazonium salt solution a mixture of18 parts of N,N-diethylamino-m-toluidine, 6 parts of aminosulphonicacid, 10 parts of glacial acetic acid and 50 parts of water is veryslowly added whilst stirring and the pH of the mixture is kept at 3.5 to4 by the addition of 30% NaOH solution. The resulting blue-grey dyestuffsuspension is then stirred for a further 2 hours, filtered and theresidue is washed with 100 parts of 10% acetic acid followed by 100parts of water and dried under vacuum at 50° C. The resulting dyestuffis a compound of formula 16a ##STR19## and dyes polyester material ablue-violet tone.

EXAMPLE 17

21.3 Parts of the product of formula 16a are dissolved in 150 parts ofdioxane at room temperature and are then reacted with 28 parts ofcyanoacetic acid methoxyethyl ester followed by a mixture of 2 partspiperidine and 2 parts of glacial acetic acid. After stirring for 20hours at 25°-30°, no starting material can be detected by thin layerchromatography.

After addition of water, the product precipitates and is filtered,washed with 100 parts of water and vacuum dried at 50°. Using a silicagel column chromatograph, a purified compound of formula 17a ##STR20##results, m.p. 135°-136°.

EXAMPLE 18

a) 18.6 Parts of 2-amino-3-cyano-4-chloro-5-formylthiophene aredissolved in 200 parts of 85% phosphoric acid. Whilst stirring, 33 partsof 40% nitrosylsulphuric acid are added dropwise and the mixture isstirred for 3 hours at about 0°.

The resulting brown diazonium salt solution is added part by part whilststirring well to a solution of 20.6 parts of3-(N,N-diethylamino)-1-acetanilide and 2 parts of aminosulphonic acid in30 parts of 5% sulphuric acid. The coupling temperature of 0°-3° isachieved by external cooling and the addition of about 200 parts of ice.The resulting dyestuff is stirred for 1-2 hours, filtered, washed withabout 300 parts of water and dried under vacuum. The resulting productis a compound of formula 18a ##STR21## which dyes polyester blue tonesand has good fastness properties.

b) Instead of using 3-(N,N-diethylamino)-1-acetanilide as the couplingcomponent in the method of Example 18a) above, a mixture of3-(N,N-di-C₂₋₄ alkylamino)-1-acetanilide (prepared by mixed alkylationof 3-amino-1-acetanilide) is used. A dyestuff mixture of formula 18b)##STR22## results. In Mixture b)1) the alkyl groups are ethyl andn-propyl and in Mixture b)2) they are ethyl and n-butyl, the molar ratioof the two alkyl groups in each mixture being 1:1.

EXAMPLES 19 to 137

Compounds of the formula ##STR23## in which the symbols are defined inTable 2 below, can be prepared by a method analogous to Examples 16, 17and 18 from suitable reactants.

    TABLE 2             Shade on EX.       polyester No. R.sub.1 R.sub.2 R.sub.5 R.sub.6     R.sub.7 R.sub.8 fibre material       19 COOC.sub.2 H.sub.5 CHO NHCOC.sub.2 H.sub.5 H C.sub.2 H.sub.5     C.sub.2 H.sub.5 violet 20 " " CH.sub.3 H " " " 21 " " NHCOOCH.sub.2     CH.sub.2 OC.sub.2 H.sub.5 H " " " 22 " " NHCOCH.sub.3 H " " " 23 " " " H C     .sub.3 H.sub.7 CH.sub.2 CH.sub.2 CH.sub.3 " 24 " " CH.sub.3 OCH.sub.3     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 OH reddish-blue 25     " " NHCOCH.sub.2 CH.sub.2 OCH.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 "     26 " " NHCOCH.sub.3 OCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2     CH.sub.2 OCOCH.sub.3 navy-blue 27 " " " OC.sub.2 H.sub.5 " " " 28 " " "     OCH.sub.2 CH.sub.2 OCH.sub.3 " " " 29 " " " OCH.sub.3 H CH.sub.2     CH.sub.2 COOCH.sub.2 CH.sub.2 OCH.sub.3 " 30 " " " H C.sub.2 H.sub.5     C.sub.2 H.sub.5 blue 31 " " NHCOC.sub.2      H.sub.5 H " " " 32 " " NHCOOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 H " "     reddish-blue 33 " " H H " CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 " 34 "     CHCHNO.sub.2 CH.sub.3 H " C.sub.2 H.sub.5 blue  35 COOC.sub.2 H.sub.5      ##STR24##      CH.sub.3 H -n-C.sub.4 H.sub.9 CH.sub.2 CH.sub.2 OH blue      36 "     ##STR25##      NHCOC.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 greenish-blue  37     " " H H " " blue      38 "     ##STR26##      CH.sub.3 H " " greenish-blue  39 " " NHCOC.sub.2 H.sub.5 H " " " 40     COOCH.sub.3 CHO CH.sub.3 H " " bluish-violet 41 " " NHCOC.sub.2 H.sub.5     H " " " 42 " O.sub.2 NHCCH " H " " blue  43 COOCH.sub.2 CH.sub.2     OCH.sub.3      ##STR27##      " H " " greenish-blue  44 CN CHO CH.sub.3 H C.sub.2 H.sub.5 C.sub.2     H.sub.5 blue 45 " " " H -n-C.sub.3 H.sub.7 -n-C.sub.3 H.sub.7 " 46 " " "     H C.sub.2 H.sub.5 -n-C.sub.4 H.sub.9 " 47 " " H H " -n-C.sub.6 H.sub.13     " 48 " " NHCOOC.sub.2 H.sub.4 OC.sub.2 H.sub.5 H " C.sub.2 H.sub.5 " 49     " " NHCOCH.sub.3 H " C.sub.3 H.sub.7 " 50 " " " H -n-C.sub.3 H.sub.7     -n-C.sub.3 H.sub.7 " 51 " " NHCOC.sub.2 H.sub.5 H " " " 52 " " " H     C.sub. 2 H.sub.5 C.sub.2 H.sub.5 " 53 " " NHCOCH.sub.2 CH.sub.2 Cl H " "     " 54 " CHO NHCOC.sub.2 H.sub.4 OCH.sub.3 H " " " 55 " " NHCOC.sub.2     H.sub.4 COOC.sub.2 H.sub.5 H " " " 56 " " NHCOCH.sub.2 COOCH.sub.3 H " "     " 57 " " NHCOCHCH.sub.2 H " " " 58 " " NHCOCH.sub.3 OCH.sub.3 " "     greenish-blue 59 " " " " CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 " 60 " "     " OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 " 61 " " " " CH.sub.2     CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 " 62 " CN CH.sub.3 H     C.sub. 2 H.sub.5 C.sub.2 H.sub.5 blue 63 CN CN CH.sub.3 H -n-C.sub.3     H.sub.7 -n-C.sub.3 H.sub.7 blue 64 " " " H -n-C.sub.4 H.sub.9 -n-C.sub.4     H.sub.9 " 65 " " " H C.sub.2 H.sub.5 " " 66 " " " H " C.sub.3 H.sub.6     OC.sub.6 H.sub.5 " 67 " CHO " H " " " 68 " " " OCH.sub.3 C.sub.2 H.sub.4     COO(CH.sub.2).sub.3 CH.sub.3 H " 69 " CN NHCOCH.sub.3 " C.sub.2 H.sub.4     COOC.sub.2 H.sub.5 H greenish-blue 70 " " " H C.sub.2 H.sub.5 C.sub.2     H.sub.5 blue 71 " " NHCOC.sub.2 H.sub.5 H -n-C.sub.3 H.sub.7 - n-C.sub.3     H.sub.7 " 72 " " NHCOCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.4      COOCH.sub.3 H " 73 " " NHCOC.sub.2      H.sub.5 OCH.sub.3 CH(CH.sub.3)C.sub.2 H.sub.5 H " 74 " " NHCOCH.sub.3 " C     .sub.2 H.sub.5 C.sub.2 H.sub.5 greenish-blue 75 " " NHCOCH.sub.3 "     CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 " 76 " " " OC.sub.2 H.sub.5     C.sub.2 H.sub.5 C.sub.2 H.sub.5 " 77 " " " " CH.sub.2 CH.sub.2      OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 " 78 " CHO OCH.sub.3 "     C.sub.2 H.sub.5 CH.sub.2CHCHCl " 79 " " OC.sub.2 H.sub.5 " C.sub.2     H.sub.5 CH.sub.2CHCH.sub.2 " 80 " " "  " CH.sub.2 CH.sub.2 OCOCH.sub.3 H     " 81 " " " " CH.sub.2 CH.sub.2 COOCH.sub.2 COOC.sub.2 H.sub.5 H " 82 " "     " " CH.sub.2 CH.sub.2 COOCH.sub.2 CHCHCl H " 83 " " " " CH.sub.2     CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " 84 CN CHO NHCOCH.sub.3     OC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CHCH.sub.2     greenish-blue 85 " CN " " " " " 86 " " " " CH.sub.2 CH.sub.2 CN " " 87 " C     HO " " " " " 88 " " " " CH.sub.2 CH.sub.2 COOCH.sub.3 " " 89 " Z.sub.1 * C     H.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 " 90 " " " H " CH.sub.2     CH.sub.2 OCOCH.sub.3 " 91 " Z.sub.2 ** " H " " " 92 " " " H " C.sub.2     H.sub.5 " 93 " " NHCOCH.sub.3 H " " " 94 CN CHO NHCOCH.sub.3 OCH.sub.3     C.sub.2 H.sub.4 CN C.sub.2 H.sub.5 greenish-blue 95 " " " " C.sub.2     H.sub.4 OCH.sub.2 CHCH.sub.2 C.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2 " 96 "     " " " -n-C.sub.4 H.sub.9 -n-C.sub.4 H.sub.9 " 97 " " " OC.sub.2 H.sub.5     " C.sub.2 H.sub.5 " 98 " " " " -n-C.sub.3 H.sub.7 -n-C.sub.3 H.sub.7 "     99 " " " OC.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2     H.sub.4 OCH.sub.3 " 100 " " " " C.sub.2 H.sub.4 COOCH.sub.3 H " 101 " "     NHCOC.sub.2 H.sub.4 OCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2     H.sub.5 " 102 " " NHCOCH.sub.3 " C.sub.2 H.sub.4 OCH.sub.3 C.sub.2     H.sub.4 OCOCH.sub.3 " 103 " " NHCOOCH.sub.3 " C.sub.2 H.sub.5 C.sub.2     H.sub.5 " 104 " " NHCOOC.sub.2 H.sub.4 OC.sub.2 H.sub.5 " C.sub.2     H.sub.5 C.sub.2 H.sub.5 " 105 " " NHCOCH.sub.3 " C.sub.2 H.sub.4     COOC.sub.2 H.sub.5 H " 106 " " NHCOCH.sub.3 " C.sub.2 H.sub.4      COOCH.sub.2 CHCH.sub.2 H " 107 " " "  OCH.sub.3 C.sub.2 H.sub.4     COOCH.sub.2C(CH.sub.3)CH.sub.2 H " 108 " " " " C.sub.2 H.sub.4      COOCH.sub.2 COOCH.sub.3 H " 109 " CN " " " H " 110 CN CHO NHCOCH.sub.3     OCH.sub.3 C.sub.2 H.sub.5 -n-C.sub.4 H.sub.9 greenish-blue 111 " CN " "     " " " 112 " CHO " H C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.5 blue 113 "     " " H " C.sub.2 H.sub.4 OCH.sub.3 " 114 " " " H (CH.sub.2).sub.3OC.sub.6     H.sub.5 C.sub.2 H.sub.5 " 115 " " " H (CH.sub.2).sub.3 COOC.sub.2     H.sub.5 " " 116 " " " H (CH.sub.2).sub.4 OCOCH.sub.3 " " 117 " " " H "     (CH.sub.2).sub.4 OCOCH.sub.3 " 118 " " H H C.sub.2 H.sub.4 OC.sub.6     H.sub.5 C.sub.2 H.sub.5 " 119 " " CH.sub.3 H C.sub.2 H.sub.4      OCH.sub.2C.sub.6 H.sub.5 " " 120 " " " H (CH.sub.2).sub.3 COOC.sub.2     H.sub.5 " " 121 " " " H (CH.sub.2).sub.3 OC.sub.6 H.sub.44-CH.sub.3 " "     122 " " " H CH.sub.2 CHOHC.sub.2 H.sub.5 " " 123 " " " H CH.sub.2     CHOHCH.sub.2 Cl " " 124 " " " H CH.sub.2 CHOHCH.sub.2 OCOCH.sub.3 " "     125 CN CHO CH.sub.3 OCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2     H.sub.4 OCOCH.sub.3 blue 126 " " " "  CH.sub.2 CHOHCH.sub.2 OC.sub.6     H.sub.5 CH.sub.3 " 127 " " " " C.sub.2 H.sub.4 COOCH.sub.2 CHCHCl H "     128 " " " " C.sub.2 H.sub.4 COOCH.sub.2 C.sub.6 H.sub.5 H " 129 " " " "     (CH.sub.2).sub.3 OC.sub.6      H.sub.5 H " 130 " " OCH.sub.3 " CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.2 "     131 " " " " CH.sub.2CHCH.sub.2 C.sub.2 H.sub.5 " 132 " " CH.sub.3 H     CH.sub.2 CH.sub.2 O(CH.sub.2).sub.3 CN " reddish blue 133 " " CH.sub.3 H C     H.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 " " 134 " " " H "     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 " 135 " "  " H CH.sub.2     CHOHCH.sub.2 OCH.sub.2 CHCH.sub.2 C.sub.2 H.sub.5 " 136 " " " H CH.sub.2     CHOHCH.sub.2 OC.sub.6 H.sub.5 " " 137 " " " H CH.sub.2 CH.sub.2      OCH.sub.2 CH.sub.2 OCOCH.sub.3 " " 138 " " " H CH.sub.2 CH.sub.2     CH.sub.2 CN " " 139 " " " H CH.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5     CH.sub.3 " 140 CN CHO CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 COOC.sub.2     H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 reddish blue 141 "     " NHCOCH.sub.3 OCH.sub.3 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 C.sub.2     H.sub.5 greenish blue 142 " " " " " CH.sub.2      CHCHCl " 143 " " NHCOC.sub.6 H.sub.5 H CH.sub. 2 CH.sub.2 OCH.sub.3     CH.sub.2 CH.sub.2 OCH.sub.3 " 144 " " NHCOCHCH.sub.2 H -n-C.sub.3     H.sub.7 C.sub.3 H.sub.7 n " 145 " " NHCOCH.sub.2 OC.sub.2 H.sub.5 H     C.sub.2 H.sub.5 C.sub.2 H.sub.5 " 146 " " NHCOCH.sub.2 OCH.sub.3 H " " "     147 " " NHCOCH.sub.3 OCH.sub.3 " CH.sub.2CHCHCl " 148 " " " OC.sub.2     H.sub.5 " CH.sub.2CHCH.sub.2 "     ##STR28##     ##STR29##

EXAMPLES 149 to 158

Compounds of the formula ##STR30##? in which K is defined in Table 3below can be prepared by a method analogous to that of Example 18 fromsuitable reactants.

                  TABLE 3                                                         ______________________________________                                        Ex.                                                                           No.  K                          Shade                                         ______________________________________                                        149                                                                                 ##STR31##                 greenish- blue                                150                                                                                 ##STR32##                 greenish- blue                                151                                                                                 ##STR33##                 greenish- blue                                152                                                                                 ##STR34##                 greenish- blue                                153                                                                                 ##STR35##                 greenish- blue                                154                                                                                 ##STR36##                 greenish- blue                                155                                                                                 ##STR37##                 greenish- blue                                156                                                                                 ##STR38##                 blue                                          157                                                                                 ##STR39##                 blue                                          158                                                                                 ##STR40##                 blue                                          ______________________________________                                    

APPLICATION EXAMPLE (a) Production of a dyeing preparation

10 g of the dyestuff of Example 18a, 9.3 g of sodium lignin sulphonateand 25 ml of demineralised water are stirred in a 150 ml beaker with atwo plate stirrer at 150-200 revs. per minute. If a homogeneous pasteresults the rate of stirring is increased to a maximum of 1500-2000revs. per minute whilst 156 g (=85 ml) of siliquarzite pearls (31-5/31-71:1) are added until a viscous grindable surface layer results. Thematerial is slowly ground whilst cooling in a continuous flowing waterbath until a fluid sample no longer produces a ring on filter paper. Thestirring is then reduced 500 revs. per minute and the mass is reactedwith a solution of 9.3 g of sodium lignin sulphonate and 20 ml ofdemineralized water as a result of which the mass becomes slightlyfluid. The mass is mixed well for 10 minutes, filtered through a glassfilter flask G2 and rinsed with 300 ml of demineralised water.

The dispersion has a pH of 9.0-9.5 and is brought to pH of 6.5 by theaddition of a 10% phosphoric acid solution.

Finally the dispersion is dried and then finely pulverized in a mill.

Instead of a dyestuff of Example 18a any one of the dyestuffs ofExamples 16 to 155 may be used in an appropriate amount.

(b) Dyeing

5 Parts of a precleaned polyester web are immersed in a high temperaturedyeing bath in 100 parts of a dyebath heated to 70°, the 100 parts ofdyebath comprising 0.05 of the above-mentioned dyeing preparation of thedyestuff of Example 18a and 2 parts ammonium sulphate, the balance beingwater and the bath is brought to pH 5 by the addition of formic acid.The dyeing apparatus is then closed and heated over 20 minutes to 130°and then maintained at this temperature for a further 60 minutes. Aftercooling the polyester web is removed from the dyebath, rinsed, soaped,rinsed again and dried. A level deep blue dyeing results with goodfastness properties. The remaining dyebath is practically colourless.

Instead of the dyeing preparations of the dyestuff of Example 18a thedyeing preparations of a dyestuff of any one of Examples 16 to 155 maybe used.

What is claimed is:
 1. A compound of the formula ##STR41## wherein K isa coupling component radical,R is halo, R₁ is cyano; (C₁₋₆alkoxy)carbonyl; (C₃₋₆ alkenyl)oxycarbonyl; C₁₋₄ alkylsulfonyl;phenylsulfonyl; (C₁₋₄ alkyl)carbonyl; benzoyl; carbamoyl; (C₁₋₄alkyl)carbamoyl; N,N-di-(C₁₋₄ alkyl)carbamoyl; phenylcarbamoyl;benzyloxycarbonyl; or (C₁₋₆ alkoxy)carbonyl, (C₃₋₆ alkenyl)oxycarbonyl,C₁₋₄ alkylsulfonyl, phenylsulfonyl or (C₁₋₄ alkyl)carbamoyl substitutedby one or two substituents independently selected from chloro, bromo,C₁₋₄ alkyl, C₁₋₄ alkoxy, hydroxy, cyano and acyl, and R₂ is formyl,cyano, --CH═C(R₄)₂ or --CH═N--OH,wherein (1) each R₄ is independentlycyano; (C₁₋₆ alkoxy)carbonyl; (C₃₋₆ alkenyl)oxycarbonyl; (C₃₋₆alkynyl)oxycarbonyl; or (C₁₋₆ alkoxy)carbonyl, (C₃₋₆ alkenyl)oxycarbonylor (C₃₋₆ alkynyl)oxycarbonyl substituted by one or two substituentsindependently selected from chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy,hydroxy, cyano and acyl, (2) one R₄ is cyano and the other is benzoyl orbenzoyl monosubstituted by (C₁₋₄ alkoxy)carbonyl, C₁₋₄ alkylsulfonyl,phenylsulfonyl, carbamoyl, (C₁₋₄ alkyl)carbamoyl, phenylcarbamoyl or(C₁₋₄ alkoxy)carbonyl, C₁₋₄ alkylsulfonyl, phenylsulfonyl or (C₁₋₄alkyl)carbamoyl substituted by one or two substituents independentlyselected from chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy, hydroxy, cyano andacyl, (3) one R₄ is hydrogen and the other is benzoyl; benzoylmonosubstituted by (C₁₋₂ alkoxy)carbonyl, halo, C₁₋₄ alkyl, nitro or(C₁₋₂ alkoxy)carbonyl substituted by one or two substituentsindependently selected from chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy,hydroxy, cyano and acyl; (C₁₋₄ alkyl)carbonyl or (C₃₋₆ alkenyl)carbonylor (4) one R₄ is nitro and other is hydrogen, methyl or ethyl, whereineach halo is independently chloro or bromo.
 2. A compound according toclaim 1 whereinR₁ is cyano; (C₁₋₆ alkoxy)carbonyl; (C₃₋₆alkenyl)oxycarbonyl; C₁₋₄ alkylsulfonyl; phenylsulfonyl; (C₁₋₄alkyl)carbonyl; benzoyl; carbamoyl; (C₁₋₄ alkyl)carbamoyl; N,N-di-(C₁₋₄alkyl)carbamoyl; phenylcarbamoyl; benzyloxycarbonyl; or (C₁₋₆alkoxy)carbonyl, (C₃₋₆ alkenyl)oxycarbonyl, C₁₋₄ alkylsulfonyl,phenylsulfonyl or (C₁₋₄ alkyl)carbamoyl monosubstituted by chloro,bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy, hydroxy, cyano, (C₁₋₄ alkyl)carbonyl or(C₁₋₄ alkoxy)carbonyl, and R₂ is formyl, cyano, --CH═C(R₄)₂ or--CH═N--OH,wherein (1) each R₄ is independently cyano; (C₁₋₆alkoxy)carbonyl; (C₃₋₆ alkenyl)oxycarbonyl; (C₃₋₆ alkynyl)oxycarbonyl;or (C₁₋₆ alkoxy)carbonyl, (C₃₋₆ alkenyl)oxycarbonyl or (C₃₋₆alkynyl)oxycarbonyl monosubstituted by chloro, bromo, C₁₋₄ alkyl, C₁₋₄alkoxy, hydroxy, cyano, (C₁₋₄ alkyl)carbonyl or (C₁₋₄ alkoxy)carbonyl,(2) one R₄ is cyano and the other is benzoyl or benzoyl monosubstitutedby (C₁₋₄ alkoxy)carbonyl, C₁₋₄ alkylsulfonyl, phenylsulfonyl, carbamoyl,(C₁₋₄ alkyl)carbamoyl, phenylcarbamoyl or (C₁₋₄ alkoxy)carbonyl, C₁₋₄alkylsulfonyl, phenylsulfonyl or (C₁₋₄ alkyl)carbamoyl monosubstitutedby chloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy, hydroxy, cyano, (C₁₋₄alkyl)carbonyl or (C₁₋₄ alkoxy)carbonyl, (3) one R₄ is hydrogen and theother is benzoyl; benzoyl monosubstituted by (C₁₋₂ alkoxy)carbonyl,halo, C₁₋₄ alkyl, nitro or (C₁₋₂ alkoxy)carbonyl monosubstituted bychloro, bromo, C₁₋₄ alkyl, C₁₋₄ alkoxy, hydroxy, cyano, (C₁₋₄alkyl)carbonyl or (C₁₋₄ alkoxy)carbonyl; (C₁₋₄ alkyl)carbonyl or (C₃₋₆alkenyl)carbonyl or (4) one R₄ is nitro and the other is hydrogen,methyl or ethyl.
 3. A compound according to claim 2 whereinR₁ is cyano,(C₁₋₆ alkoxy)carbonyl, (C₃₋₆ alkenyl)oxycarbonyl, C₁₋₄ alkylsulfonyl,phenylsulfonyl, (C₁₋₄ alkyl)carbonyl, benzoyl, carbamoyl, (C₁₋₄alkyl)carbamoyl, N,N-di-(C₁₋₄ alkyl)carbamoyl, phenylcarbamoyl orbenzyloxycarbonyl, and R₂ is formyl, cyano, --CH═C(R₄)₂ or--CH═N--OH,wherein (1) each R₄ is independently cyano, (C₁₋₆alkoxy)carbonyl, (C₃₋₆ alkenyl)oxycarbonyl or (C₃₋₆ alkynyl)oxycarbonyl,(2) one R₄ is cyano and the other is benzoyl or benzoyl monosubstitutedby (C₁₋₄ alkoxy)carbonyl, C₁₋₄ alkylsulfonyl, phenylsulfonyl, carbamoyl,(C₁₋₄ alkyl)carbamoyl or phenylcarbamoyl, (3) one R₄ is hydrogen and theother is benzoyl; benzoyl monosubstituted by (C₁₋₂ alkoxy)carbonyl,halo, C₁₋₄ alkyl or nitro; (C₁₋₄ alkyl)carbonyl or (C₃₋₆alkenyl)carbonyl or (4) one R₄ is nitro and the other is hydrogen,methyl or ethyl.
 4. A compound according to claim 2 having the formula##STR42## wherein K" is ##STR43## wherein R₅ is hydrogen; C₁₋₂ alkyl;C₁₋₂ alkoxy; formamido; (C₁₋₄ alkyl)carbonylamino; (C₁₋₄alkyl)carbonylamino the alkyl group of which is monosubstituted byhydroxy, chloro, bromo, C₁₋₄ alkoxy, phenyl, phenoxy, benzyloxy or (C₁₋₂alkoxy)carbonyl; benzamido; acryloylamino; aminocarbonylamino; (C₁₋₄alkyl)aminocarbonylamino; (C₁₋₄ alkoxy)carbonylamino; (C₁₋₄alkoxy)carbonylamino the alkoxy group of which is monosubstituted byC₁₋₂ alkoxy or phenyl; C₁₋₂ alkylsulfonylamino; phenylsulfonylamino;N,N-di-(C₁₋₂ alkyl)aminosulfonylamino; fluoro; chloro or bromo,R₆ ishydrogen, fluoro, chloro, bromo, C₁₋₂ alkyl, C₁₋₄ alkoxy or (C₁₋₂alkoxy)ethoxy, with the proviso that when R₅ is fluoro, chloro or bromo,R₆ is other than fluoro, chloro and bromo, R₇ is hydrogen; C₁₋₁₀ alkyl;C₂₋₁₀ alkyl monosubstituted by chloro, bromo, hydroxy, cyclohexyl,thiocyanato, cyano, (C₁₋₄ alkyl)carbonyl, (C₁₋₄ alkoxy)carbonyl,formyloxy, (C₁₋₁₀ alkyl)carbonyloxy, chloro(C₁₋₃ alkyl)carbonyloxy,bromo(C₁₋₃ alkyl)carbonyloxy, (C₁₋₁₀ alkoxy)carbonyloxy, (C₁₋₂alkoxy)ethoxycarbonyloxy, (C₃₋₄ alkenyl)oxycarbonyl,chloroallyloxycarbonyl, bromoallyloxycarbonyl, C₃₋₄ alkenyloxy,chloroallyloxy, bromoallyloxy, C₃₋₄ alkynyloxy, benzoyloxy, C₁₋₁₀alkoxy, phenyl, phenoxy, phenyl(C₁₋₄ alkoxy), (C₁₋₂alkoxy)ethoxycarbonyl or benzyloxycarbonyl; C₂₋₁₀ alkyl substituted bytwo substituents selected from chloro, bromo, hydroxy, formyloxy, (C₁₋₄alkyl)carbonyloxy, chloro(C₁₋₃ alkyl)carbonyloxy, bromo(C₁₋₃alkyl)carbonyloxy, (C₁₋₄ alkoxy)carbonyloxy, (C₁₋₂alkoxy)ethoxycarbonyloxy, chloroallyloxycarbonyl, bromoallyloxycarbonyl,C₃₋₄ alkynyloxy and (C₁₋₂ alkoxy)ethoxycarbonyl; (C₁₋₄ alkoxy)C₂₋₆ alkylthe alkyl moiety of the alkoxy group of which is monosubstituted bychloro, bromo, cyano, C₁₋₄ alkoxy, (C₁₋₄ alkoxy)carbonyl, (C₁₋₄alkoxy)carbonyloxy or (C₁₋₄ alkyl)carbonyloxy; β-[(C₁₋₄alkoxy)carbonylmethoxycarbonyl]ethyl; C₃₋₄ alkenyl; C₃₋₄ alkenylmonosubstituted by phenyl, chloro or bromo; propynyl; C₅₋₇ cycloalkyl;cyclohexyl monosubstituted, disubstituted or trisubstituted by methyl;phenyl; phenyl monosubstituted by chloro, bromo, nitro, C₁₋₄ alkoxy ormethyl or disubstituted or trisubstituted by methyl; or β-hydroxypropylmonosubstituted by γ-C₁₋₄ alkoxy, γ-C₃₋₄ alkenyloxy or γ-phenoxy, R₈ ishydrogen; C₁₋₁₀ alkyl; C₂₋₁₀ alkyl monosubstituted by chloro, bromo,hydroxy, cyano, thiocyanato, (C₁₋₁₀ alkyl)carbonyl, (C₁₋₁₀alkoxy)carbonyl, formyloxy, (C₁₋₁₀ alkyl)carbonyloxy, chloro(C₁₋₄alkyl)carbonyloxy, bromo(C₁₋₄ alkyl)carbonyloxy, (C₁₋₁₀alkoxy)carbonyloxy, (C₁₋₂ alkoxy)ethoxycarbonyloxy, (C₃₋₄alkenyl)oxycarbonyl, chloroallyloxycarbonyl, bromoallyloxycarbonyl, C₃₋₄alkenyloxy, chloroallyloxy, bromoallyloxy, C₃₋₄ alkynyloxy, benzoyloxy,C₁₋₁₀ alkoxy, phenyl, phenoxy, phenyl(C₁₋₄ alkoxy), carbamoyl, (C₁₋₄alkyl)carbamoyl, N,N-di-(C₁₋₄ alkyl)carbamoyl, phenylcarbamoyl, (C₁₋₄alkyl)carbamoyloxy, N,N-di-(C₁₋₄ alkyl)carbamoyloxy, phenylcarbamoyloxy,phthalimidyl-2, succinimidyl-2, saccharinyl-2, pyridyl,benzothiazolyl-2-mercapto, (C₁₋₂ alkoxy)ethoxycarbonyl orbenzyloxycarbonyl; C₂₋₁₀ alkyl substituted by two substituents selectedfrom chloro, bromo, hydroxy, formyloxy, (C₁₋₄ alkyl)carbonyloxy,chloro(C₁₋₃ alkyl)carbonyloxy, bromo(C₁₋₃ alkyl)carbonyloxy, (C₁₋₄alkoxy)carbonyloxy, (C₁₋₂ alkoxy)ethoxycarbonyloxy,chloroallyloxycarbonyl, bromoallyloxycarbonyl, C₃₋₄ alkynyloxy and (C₁₋₂alkoxy)ethoxycarbonyl; (C₁₋₄ alkoxy)C₂₋₄ alkyl the alkyl moiety of thealkoxy group of which is monosubstituted by chloro, bromo, cyano, C₁₋₄alkoxy, (C₁₋₄ alkoxy)carbonyl, (C₁₋₄ alkoxy)carbonyloxy or (C₁₋₄alkyl)carbonyloxy; C.sub. 3-4 alkenyl or C₃₋₄ alkenyl monosubstituted byphenyl, chloro or bromo, or --NR₇ R₈ is piperidino or morpholino, and R₉is hydrogen, C₁₋₄ alkyl, phenyl or phenyl substituted by one or twosubstituents selected from methyl, methoxy and chloro, R₁ ' is cyano,(C₁₋₄ alkoxy)carbonyl, (C₃₋₄ alkenyl)oxycarbonyl, (C₁₋₄ alkoxy) (C₂₋₄alkoxy)carbonyl, benzyloxycarbonyl, (C₁₋₄ alkyl)carbamoyl, C₁₋₄alkylsulfonyl or phenylsulfonyl, and R₂ ' is formyl, cyano or --CH═C(R₄')₂,wherein each R₄ ' is independently cyano, (C₁₋₆ alkoxy)carbonyl,(C₃₋₆ alkenyl)oxycarbonyl or 2-(C₁₋₄ alkoxy)ethoxycarbonyl or one R₄ 'is nitro and the other is hydrogen.
 5. A compound according to claim 4having the formula ##STR44## wherein R₁ '" is cyano or (C₁₋₂alkoxy)carbonyl,R₂ " is formyl or cyano, R₅ ' is hydrogen, C₁₋₂ alkyl or(C₁₋₂ alkyl)carbonylamino, R₆ ' is hydrogen or C₁₋₂ alkoxy, R₇ ' is C₁₋₆alkyl, (C₁₋₄ alkoxy)C₂₋₄ alkyl, (C₃₋₄ alkenyl)oxy(C₂₋₄ alkyl), (C₁₋₂alkyl)carbonyloxy(C₂₋₄ alkyl), (C₁₋₄ alkoxy)carbonyl(C₂₋₄ alkyl), allyl,(C₁₋₂ alkoxy)carbonyloxy(C₂₋₄ alkyl) or phenoxy(C₂₋₄ alkyl), and R₈ ' ishydrogen, C₂₋₄ alkyl, (C₁₋₄ alkoxy)C₂₋₄ alkyl, (C₃₋₄ alkenyl)oxy(C₂₋₄alkyl), allyl, hydroxy(C₂₋₄ alkyl), (C₁₋₂ alkoxy)carbonyloxy(C₂₋₄ alkyl)or (C₁₋₂ alkyl)carbonyloxy(C₂₋₄ alkyl).
 6. A compound according to claim5 having the formula ##STR45## wherein K"" is 2-methyl-4-[N,N-di-(C₂₋₄alkyl)amino]phenyl,2-methyl-4-(N-ethyl-N-γ-ethoxycarbonylpropylamino)phenyl,2-methyl-4-(N-ethyl-N-γ-phenoxypropylamino)phenyl,2-acetamido-4-(N-β-ethoxycarbonylethylamino)-5-ethoxyphenyl,2-acetamido-4-(N-ethyl-N-allylamino)-5-ethoxyphenyl,2-methyl-4-(N-ethyl-N-β-hydroxybutylamino)phenyl,2-acetamido-4-[N,N-di-(C₂₋₃ alkyl)amino]phenyl or2-acetamido-4-[N,N-di-(C₂₋₄ alkyl)amino]-5(C₁₋₂ alkoxy)phenyl.
 7. Acompound according to claim 6 wherein K"" is 2-methyl-4-[N,N-di-(C₂₋₄alkyl)amino]phenyl.
 8. A compound according to claim 6 wherein K"" is2-acetamido-4-[N,N-di-(C₂₋₃ alkyl)amino]phenyl.
 9. A compound accordingto claim 6 wherein K"" is 2-acetamido-4-[N,N-di-(C₂₋₄alkyl)amino]-5-(C₁₋₂ alkoxy)phenyl.
 10. The compound according to claim6 wherein K"" is2-methyl-4-(N-ethyl-N-γ-ethoxycarbonylpropylamino)phenyl.
 11. Thecompound according to claim 6 wherein K"" is2-methyl-4-(N-ethyl-N-γ-phenoxypropylamino)phenyl.
 12. The compoundaccording to claim 6 wherein K"" is2-acetamido-4-(N-β-ethoxycarbonylethylamino)-5-ethoxyphenyl.
 13. Thecompound according to claim 4 having the formula ##STR46##
 14. Thecompound according to claim 8 having the formula ##STR47##
 15. Thecompound according to claim 5 having the formula ##STR48##
 16. Thecompound according to claim 5 having the formula ##STR49##
 17. Thecompound according to claim 4 having the formula ##STR50##
 18. A processfor dyeing a substrate comprising applying to a substrate a compoundaccording to claim
 1. 19. A substrate dyed with a compound according toclaim 1.